Zeolite-based composites

Baglio V, Arico S, di Blasi A, Antonucci PL, Nannetti F, and Tricoli V. Zeolite-based composite membranes for high temperature direct methanol fuel cells. J Appl Electrochem 2005 35 207-212. 

Controlled removal of the template is especially important when zeolite based membranes are involved consisting of a continuous MFI layer on a ceramic or sintered metal support (ref. 14). In these novel composite ceramic membranes the formation of cracks during template removal would be detrimental. The unique properties (ref. 14) of metal-supported MFl-layer membranes prove that indeed crack formation can be essentially prevented. 

The low H/C-ratio of FCC feed derived from liquefied biomass led to low conversion and poor gasoline selectivity. Addition of alumina to the matrix resulted in a catalyst more active for heavy oil cracking but with a poor selectivity. Alumina-montmorillonite catalysts showed activities for heavy oil cracking comparable to that of a conventional, zeolite based, cracking catalyst. Effects of matrix composition and zeolite type on the heavy oil cracking performance are discussed. 

Carbonium ions and isoparaffins are formed by hydride ion abstraction and hydride ion transfer reactions. This mechanism has been described for HF.SbFg (5). Isomerization of n-paraffins over monofunctional acidic catalysts has also been claimed for mordenite (6, 7), for sieve Y (8), and for the base of the catalyst of undisclosed composition applied in the isomerization process using a noble metal on an acidic zeolite base (3). 

During the last few years, ceramic- and zeolite-based membranes have begun to be used for a few commercial separations. These membranes are all multilayer composite structures formed by coating a thin selective ceramic or zeolite layer onto a microporous ceramic support. Ceramic membranes are prepared by the sol-gel technique described in Chapter 3 zeolite membranes are prepared by direct crystallization, in which the thin zeolite layer is crystallized at high pressure and temperature directly onto the microporous support [24,25],... 

The in situ membrane growth technique cannot be applied using the zeolite-based ceramic porous membrane as support, under hydrothermal conditions in a solution containing sodium hydroxide. The high pH conditions will cause membrane amorphization and lead to final dissolution. Therefore, we tried to synthesize an aluminophosphate zeolite such as AlP04-5 [105] over a zeolite porous ceramic membrane. For the synthesis of the AlP04-5-zeolite-based porous membrane composite, the in situ membrane growth technique [7,13,22] was chosen. Then, the support, that is, the zeolite-based porous ceramic membrane, was placed in contact with the synthesis mixture and, subsequently, subjected to a hydrothermal synthesis process [18]. The batch preparation was as follows [106] ... 

It is evident that the ceramic membrane, which is represented in the XRD pattern (see Figure 10.6) by the amorphous component of the XRD profile, was covered by the AlP04-5 molecular sieve, since the crystalline component of the obtained XRD pattern fairly well coincides with the standards reported in the literature [107]. Consequently, the porous support was successfully coated with a zeolite layer, which was shaped by the hydrothermal process as previously described. Thus, a composite membrane, that is, an AlP04-5 molecular sieve thin film zeolite-based ceramic, was produced. 

First, although the use of bulky organic bases clearly shifts the silicate equilibrium to the DnR species, there may be a large amount (up to more than 90%) of polymeric species present in silicate solutions. This is true especially at low OH/Si ratios (<0.5) or high Si concentrations (>2), i.e., normal values for a zeolite synthesis composition. This range of polymeric silicates cannot at present be characterized satisfactorily, and the presence of zeolite precursor species other than DnR silicates in this range cannot be excluded. 

The influence of zeolites and iron oxide on the antistatic properties of PVC based composites have been established (426). 

Table 7 lists the currently known aluminosilicate zeolites based upon definition by their unique frameworks following Baerlocker, Baerlocher, Meier, and Olson. It also contains typical unit cell compositions, the lUPAC code, and type localities, but is restrictive in the sense that it does not consider the mineralogical aspects of the study of zeolites. The authoritative body for these is the Subcoimnittee for Zeolite NomenclaMe of the Conunission on New Minerals and Mineral Names of the International Mineralogical Association. Their guidelines have been cited in a recent book on natural zeolites by Tschemich, as follows. 

Sophisticated catalysts, such as ZSM-5 or HZSM-5 [22] and other zeolites are also suggested in numerous papers, e.g. KEY [23], HY and H-mordenite [24], Re-zeolite-based Engelhardt FCC commercial catalyst [25], and steamed commercial zeolite catalyst [26]. These investigations are mainly devoted to fundamental studies and the correlation between feed composition, catalyst properties, process parameters and efficiency connected with prodnct distribution. Iron supported on silica-alumina, mesoporous silica and active carbons serves as the next example of materials applied in the waste plastics cracking [27, 28]. On the other hand, according to some results [29] application of cracking catalysts such as Zn-13X, Fe-5A and CoMo-HY are ineffective in waste plastics cracking. 

The synthesis of the / NA/AlP04-5 and that of the cadmium sulfide/zeolite Y composites are typical of the preparation methods used to generate zeotype-based host-guest materials. These usually involve multi-step syntheses. Typical reaction sequences are ... 

Zeolite materials are used commercially as shape/ size selective catalysts in the petrochemical and petroleum refining industry, and as molecular sieving separation media for gases and hydrocarbons. For both applications, zeolites are used in powder composite form such as pellets and granules. In this entry, we focus on zeolite membranes. We define zeolite membranes as a continuous phase of zeolite-based materials (pure zeolite or composite) that separate two spaces. Zeolite membranes are generally uniform thin films attached to a porous or a nonporous substrate. They can also be self-standing without a substrate. Note that we have included zeolite films and layers on nonporous substrate in this entry because we believe many of the synthesis strategies and applications reported for those nonporous substrates are easily transferred to a porous substrate to prepare a zeolite membrane. 

Pyridine bases such as 3-picoline and MEP are predominantly manufactured by the Chichibabin reaction, where a mixture of aldehydes or ketones is reacted with ammonia. Thus, formaldehyde, acetaldehyde and ammonia react in the gas phase to produce a mixture of pyridine and 3-picoline. By choosing the appropriate aldehyde or ketone, catalyst and phase (liquid or gas phase), the composition of the mixture can be varied at will, depending on the desired end-product. In the gas phase, silica alumina catalysts are often used, while in the liquid phase acid catalysts based on phosphoric or acetic acid are employed. In the 1990s, Reilly patented MET and BEA-based zeolite catalyst compositions for ammonia-aldehyde conversions to pyridine, picolines and alkyl pyridines. 

In zeolite-based catalysts a number of factors can influence performance (activity, selectivity, life). These have been reviewed recently by Venuto [3]. In a previous study we have explored the impact of surface composition [4] (Si02/Al203 ratio) on catalytic performance, in TDP, and this paper aims to extend this study by describing the effect of framework structure in the same reaction. 

Regarding the composition of diesel exhaust gases (containing amongst others water and SO2), developing a stable, zeolite based diesel exhaust deNOx catalyst is a challenging task. Zeolites can show dealumination under hydrothermal conditions accompanied by a loss of active material furthermore SO2 can also cause deactivation. Many authors already have reported on the hydrothermal stability of zeolite SCR catalysts [e.g. 7-9] and also some papers exist on the stabilization with respect to hydrothermal deactivation of zeolite SCR catalysts by the choice of proper cations [10-13]. A small number of articles describes the influence of SO2 on zeolite SCR catalysts [14-17]. The current paper gives the results of measurements on both the short term hydrothermal stability and the influence of SO2 on CeNa-MOR and CeH-ZSM-5 zeolite catalysts. 

Composition of the inorganic framework can be varied just like the surfactant use has been expanded beyond the original cationic species. The number of explored element combinations has been enormous and often driven by specific catalytic needs and prior experience with amorphous or crystalline compositions [37]. One of the leading approaches was doping of silica formulation with appropriate activating clement, such as aluminum (lo impart acidity) and titanium or vanadium for redox potential. Based on analogy of AlPO s and SAPO s to zeolites these compositions were also synthesized in the mesoporous form as were other non-silica inorganic oxides and their combinations [38]. Pure metal mesoporous product was obtained via the pre-formed liquid crystal route 1391. 

One of the first zeolite based membranes were composite membranes, obtained by dispersion of zeolite crystals in dense polymeric films in order to make zeolite filled polymeric membranes [59,60,61], These membranes have been developed at the end of the 80 s for both gas separation and pervaporation. The clogging of zeolite pores by the matrix and the quality of the interface between the zeolite crystals and the polymer matrix (non-selective diffusion pathways) were key points. 

O Connor has written surveys of both homogeneous and heterogeneous catalysis while the reviews of Skupinska and Al-Jarallah et focus particularly on homogeneous catalysis. Recently, Minachev et al. have written about their work on the catalytic and physicochemical properties of the zeolites based on pentasils for oligomerizing lower olefins and paraffins into a mixture of aliphatic hydrocarbons of the composition Ce-Cio or into a concentrate of aromatic hydrocarbons, depending on the reaction conditions. 

Zeolites can be classified in many ways. Two convenient methods are on the basis of pore size and chemical composition, that is, the Si/Al ratio. The pore diameter is determined by the size of the free apertures in the structure, which is dependent on the number of T atoms (T = Si or Al) that form the aperture. Table 10.1 summarizes some examples of zeolites based on pore size classification. It should be noted that the values typically reported in the literature are determined by crystallographic studies. While these numbers are good guides, it is important to note that the actual pore size depends on many factors, including temperature, firamework composition, and the type of extra-framework cations present in the zeolite. These factors can lead to subtle changes in effective pore sizes and subsequently large changes in material properties (adsorption/reactivity). 

Table 10.2 summarizes some examples of zeolites based on their classification by chemical composition. Low-silica zeolites (Si/Al < 5) are synthesized in basic conditions (pH >13) using a silicon source, an aluminum source, and alkali hydroxides at moderate temperatures, typically less than 120°C. The identity of the alkaU species used is a determining factor in which phase is obtained from synthesis, as the relative rates of (alumino)silicate hydrolysis and condensation reactions are dependent on the identity of the alkali cation. It is also believed that hydrated alkali cations effectively direct the assembly of (alumino)silicate precursors into fuUy connected three-dimensional structures. Sodium and potassium hydroxide have been used most frequently in low-silica zeolite syntheses due to their low cost and high solubility in... 

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